CN107949775A - The frequency registration bias of quantitative spectra determining and correcting - Google Patents
The frequency registration bias of quantitative spectra determining and correcting Download PDFInfo
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- CN107949775A CN107949775A CN201680045262.7A CN201680045262A CN107949775A CN 107949775 A CN107949775 A CN 107949775A CN 201680045262 A CN201680045262 A CN 201680045262A CN 107949775 A CN107949775 A CN 107949775A
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Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
- G01J3/28—Investigating the spectrum
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/27—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands using photo-electric detection ; circuits for computing concentration
- G01N21/274—Calibration, base line adjustment, drift correction
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
- G01J3/28—Investigating the spectrum
- G01J2003/283—Investigating the spectrum computer-interfaced
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
- G01J3/28—Investigating the spectrum
- G01J2003/2866—Markers; Calibrating of scan
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/39—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using tunable lasers
Abstract
When the spectroscopic analysis system of sample fluid deviates standard calibration state, the live spectrum quantification frequency registration bias collected during analysis to the spectroscopic analysis system.Live frequency spectrum is corrected based on frequency registration bias using at least one spectral shift technology, and at least one analyte concentration by live frequency spectrum designation is calculated using calibrated live frequency spectrum.Describe relevant system, method and article.
Description
Cross reference to related applications
This application involves and require submitted within 3rd with August in 2015 U.S. Patent application No.14/817,119 it is preferential
Power, entire contents are incorporated herein by reference herein.
Technical field
The disclosure relates generally to spectrum analysis, and more particularly relates to realize and keep from spectroanalysis instrument
The accurate and reproducible frequency of absorption spectra data and/or the method for wavelength registration.
Background technology
The deterioration of the hardware of spectroscopic analysis system, drift one or more of not reproducible can influence frequency and ripple
Long registration, and therefore influence the accuracy and repeatability of measurement carried out using this system.These effects are in spectrum analysis
It is typically inevitable in practical application.The hardware of spectroscopic analysis system can include light source (such as lamp, laser etc.), electricity
Sub- device, optics, mechanical part etc..Realize and keep the accurate and reproducible frequency of absorption spectra data and wavelength to match somebody with somebody
It will definitely be the significant consideration in quantitative spectrography.
The currently available method for solving the problems, such as these includes the use of the reference of a row (in-line) or the configuration of beam splitting path
Room (reference cell) technology, uses inspecting periodically for the frequency and/or wavelength of verification gas or admixture of gas registration
And be present in target analytes in sample fluid and/or another " background " compound the strong spectral peaks of one or more peak with
Track, to correct frequency registration bias.However, with reference to room or verification room (for example, such as in jointly owned United States Patent (USP) No.8,
Described in 358,417, it is incorporated herein by reference) it may require that extra hardware installation and analysis system may be increased and set
The complexity of meter.Checked using the regular frequency or wavelength of one or more calibrating gas or admixture of gas registration except that can disappear
Outside the standardized fluid supply of consumption, it usually needs for the target analytes containing concentration known or another absorption target ripple
The compound (its there may be or may be not present in process sample fluid) of light in long region fluid (such as gas or
Liquid) handover mechanism.This method can also interrupt continuous process measurement, this can cause serious when execution system is verified
Measure the blindness time.Peak tracking may be easily by background fluid composition transfer and pressure and temperature effect.In addition, though peak
Tracking can usually be used for correcting linear frequency registration bias, but it is usually carried in terms of correction of Nonlinear frequency registration bias
The benefit of confession is seldom.
The content of the invention
In one aspect of the invention, a kind of method includes：When the spectroscopic analysis system of sample fluid deviates standard calibration
During state, quantify the frequency registration bias for the live frequency spectrum that the spectroscopic analysis system is collected during analysis, use at least one
Spectral shift technology is based on frequency registration bias and corrects live frequency spectrum, and calculates by the concentration of the analyte of live frequency spectrum designation.
The calculating includes calibration set of algorithms being applied to calibrated live frequency spectrum.
In one aspect, a kind of method includes：When the spectroscopic analysis system of sample fluid deviates standard calibration state, amount
Change the frequency registration bias for the live frequency spectrum that the spectroscopic analysis system is collected during analysis, use at least one spectral shift skill
Art is based on frequency registration bias and corrects live frequency spectrum, and is calculated using calibrated live frequency spectrum by live frequency spectrum designation at least
A kind of concentration of analyte.
In optional modification, one or more of following characteristics can be included with any feasible combination.For example, one
In a little realizations, spectroscopic analysis system can alternatively include at least one of lasing light emitter and non-laser source and quantify scene frequency
The detector of spectrum, at least one of the lasing light emitter and non-laser source are arranged to pass the beam through sample fluid at least once.
In the realization that spectroscopic analysis system includes lasing light emitter, lasing light emitter can alternatively include semiconductor laser, tunable two pole
Pipe laser, quantum cascade laser, swash with interior cascaded laser, horizontal cavity emitting laser, vertical-cavity-face emitting semiconductor
Light device, distributed feedback laser, distribution Bragg reflection device laser, external-cavity diode laser, gas discharge laser
One or more in device, liquid laser and solid state laser.In the realization that spectroscopic analysis system includes non-laser light source,
Non-laser light source can alternatively include light emitting diode, incandescent source, heat source, discharge source, laser assisted source, Laser Driven
Plasma source, fluorescence source, super generating light source, amplification spontaneous emission (ASE) source, super continuous source, wide spectral sources, and have can
Dim the one or more in the wide tunable QCL sources of grid-type waveguide filter.
Spectroscopic analysis system can alternatively further comprise that sample room (sample cell) is used to pass through sample in light beam
Fluid at least once while accommodate sample fluid.Alternatively, spectroscopic analysis system can alternatively further comprise free sky
Between volume, wherein light beam through sample fluid at least once while sample fluid be located in the free space volume.To existing
The quantization of the frequency registration bias of field spectrum can alternatively include calibration set of algorithms being applied to live frequency spectrum, and/or to existing
The quantization of the frequency registration bias of field spectrum can alternatively include the use of at least one frequency for being included in calibration algorithm concentration
Registration bias function.
Calibration algorithm collection can alternatively include the concentration function for spectroscopic analysis system, and quantization can be alternatively
Including mathematically changing the frequency registration bias of live frequency spectrum to produce the change of predetermined quantity, calculate and answered by concentration function
For each change of one or more confidence indexs for live frequency spectrum after each change of live frequency spectrum, and will be every
The compositional modeling of a confidence index or more than one confidence index is the one-variable function of frequency registration bias, with mathematically true
Surely the combination of confidence index or multiple confidence indexs minimum or maximized optimum frequency registration bias are made.Concentration function can be with
Being optionally based on does not include the unmodified calibration spectrum data set of manually generated frequency registration bias spectrum.Analyte is dense
Calculating for degree can alternatively include for concentration function being applied to the live spectral change corresponding to optimum frequency registration bias.
Calibration algorithm collection can alternatively include the calibration data based on the standard calibration state for representing spectroscopic analysis system
The output of the computing engines of the multi-variables analysis of collection.Calibration data set can be optionally included in design time pass through mathematics is inclined
Move the manually generated frequency registration bias spectrum for being applied to generate using the calibration spectrum that calibration sample is collected.To live frequency
The quantization of the frequency registration bias of spectrum can alternatively include：The frequency registration of live frequency spectrum is calculated using calibration algorithm collection
Characteristic index, and by the way that the characteristic index measurement index registering with the frequency determined by live frequency spectrum to be compared to quantify
The frequency registration bias of live frequency spectrum.The measurement index of frequency registration can alternatively include one or more spectral signatures and/
Or the interval between one or more spectral signatures.
Correction can alternatively include the use of measuring state frequency registration of at least one spectral shift technology based on quantization
The live frequency spectrum of deviation correction.At least one spectral shift technology can alternatively include linear deflection, non-linear shift, survey
Measure the stretching of frequency spectrum and measure at least one of compression of frequency spectrum.At least one spectral shift technology can alternatively with
Pure mathematics mode, is answered via the one or more in the combination that hardware tunes and is tuned by using Mathematical Correction and hardware
With.At least one spectral shift technology can be alternatively applied to one or more of whole scene frequency spectrum or live frequency spectrum
A particular.
The article of the system and method consistent with this method and the machine readable media including visibly realizing is described,
The machine readable media is operable such that one or more machines (such as computer etc.) cause operate as described herein.Class
As, computer system is also described, it can include computer hardware, such as one or more processors and coupling
To the memory of one or more processors.Memory can include so that one or more processors execution is described herein
One or more programs of one or more operation.
The details of one or more modifications of this theme is elaborated in the the accompanying drawings and the following description.Other of this theme are special
Advantage of seeking peace will be apparent from specification, drawings and the claims.
Brief description of the drawings
The attached drawing for being incorporated to this specification and forming the part of this specification shows certain aspects of the invention, and with
Specification helps explain some principles associated with disclosed embodiment together.Wherein,
Fig. 1 shows the exemplary figure for illustrating spectral measurement system according to the present invention；
Fig. 2 shows the process flow diagram flow chart for realizing consistent method characteristic of explanation and the present invention；
Fig. 3 shows another process flow diagram flow chart for realizing consistent method characteristic of explanation and the present invention；
Fig. 4 shows another process flow diagram flow chart for realizing consistent method characteristic of explanation and the present invention；
Fig. 5 shows the figure of explanation and the relevant feature of generation for realizing consistent calibration algorithm collection of the present invention；
Fig. 6 shows another process flow diagram flow chart for realizing consistent method characteristic of explanation and the present invention；
Fig. 7 shows the figure of explanation and the relevant feature of generation for realizing consistent calibration algorithm collection of the present invention；
Fig. 8 shows the figure of explanation and the relevant feature of generation for realizing consistent calibration algorithm collection of the present invention；
Fig. 9 shows another process flow diagram flow chart for realizing consistent method characteristic of explanation and the present invention；
Figure 10 shows the figure of explanation and the relevant feature of generation for realizing consistent concentration model of the present invention；
Figure 11 shows that explanation mathematically changes sample spectra to produce the consistent predetermined quantity realized with the present invention
The exemplary chart of change；And
Figure 12 shows that explanation determines the exemplary chart of the optimal confidence index consistent with the realization of the present invention.
In practice, similar reference numeral represents similar structure, feature or element.
Embodiment
It is consistent with the realization of the present invention, it can simulate and correct possibility using multivariable technique as described herein
The frequency registration bias effect occurred in spectroscopic analysis system, without changing the existing hardware of spectroscopic analysis system, making
The dependence tracked with the peak of compound in regular (or non-periodically) the instrument verification of calibrating gas or convection body flow samples.With this
Kind mode, it is possible to achieve and keep stable, reliable and reproducible measurement.
Although herein in regard to use wavelength or frequency modulation(PFM) tunable diode laser absorption spectroscopy instrument (TDLAS) or adjustable
The Harmonic Spectrum technology of humorous lasing spectrum of semiconductor lasers instrument come describe the present invention example implementation, it will be appreciated that, with the present invention
Consistent method can be used in combination with the analytical instrument or method for being related to any quantitative spectra method, including but not limited to inhale
Sending and receiving are penetrated and fluorescence spectroscopy, such as fourier-transform infrared (FTIR) spectroscopy, non-dispersive infrared (NDIR) spectroscopy, chamber
Enhanced spectrum (CES), cavity ring-down spectroscopy (CRD), collection coelosis output spectrum (ICOS), photoacoustic spectroscopy, Raman spectrum
Learn etc..
Fig. 1 shows the figure of the exemplary spectroscopy analysis system 100 according to the disclosure, it includes appearing in and the present invention
Consistent other spectroscopic analysis systems of realization in feature.Spectroscopic analysis system 100 can include with one or more targets
Wavelength or the light source 102 operated in a wavelength range.Light source 102 provides the continuous light beam projected along light path 104 or pulse
Radiate (for example, with the light of visible ray, ultraviolet, infrared ray etc. or other types of electromagnetic radiation), light path 104 is by detector
The volume 106 of sample fluid is passed through before 110 detections.Light source 102 can alternatively include one or more lasers, such as half
Conductor laser, tunable diode laser (TDL), quantum cascade laser (QCL), with interior cascaded laser (ICL), water
Flat chamber emitting laser (HCSEL), vertical-cavity-face emitting semiconductor laser (VCSEL), distributed feedback laser (DFB), point
Cloth Bragg reflection device laser (DBR), external-cavity diode laser, gas discharge laser, liquid laser, solid
Laser etc..Light source 102 or can also alternatively include one or more non-laser light sources, for example, such as light emitting diode
(LED), lamp and/or it is another can be interacted by nonlinear optics and/or pass through spectral filtering produce frequency-adjustable light
Device.The example of lamp can include but is not limited to the plasma source of heat source, discharge source, laser assisted or Laser Driven, fluorescence
Source, super generating light source, spontaneous emission (ASE) source, super continuous source and the wide spectral sources of amplification.It is also included within the scope of the present disclosure
It is that (such as can such as be obtained with tunable optical grid-type waveguide filter from the Redshift Systems of the Burlinton of Massachusetts
Those) the QCL sources that can be tuned extensively example.
Detector 110 can include photodiode, photoelectric detector, photo acoustic detector or for light path at least across
Volume 106 once detects one or more of other devices or structure of the radiation intensity that light source 102 is sent afterwards.In some realities
In existing, volume 106 can be contained in the sample room 112 with one or more windows or other openings 114, light path 104
Volume 106 is entered and left by the one or more window or other openings 114.Sample room 112 can be as shown in Figure 1 stream
Through chamber, wherein fluid flows into sample room 112 via entrance 116, and passes through the outflow sample room 112 of outlet 120.The present invention's
Again in other realizations, analysis system can be omitted sample room, and can alternatively configure so that light path is in light source 102 and detection
At least across unlimited (such as unbounded or unclosed) space (such as in stacking, open when being crossed between device 110
Air is medium) once.In the open approach system consistent with the realization, light path can alternatively include via being arranged in opening
In spatial volume or the one or more of the mirror adjacent with open space volume or other reflecting surfaces reflects.
In addition to shown in Fig. 1, other configurations are also possible.It is, for example, possible to use mirror, beam splitter or passing through
Change other geometric parameters (such as position of light source 102 and/or detector 110) to establish the path length of light path 104, it is described
Path length is the distance that the continuous light beam of radiation or pulse pass through sample fluid, in addition, sample volume may be embodied in light source
The open approach of non-close between 102 and detector 110.Depending on one or more analytes to be measured, expected presence
One or more analytes concentration range and may interfere with measurement in sample accuracy other compounds or material
The presence of material, continuous light beam or pulsed light can by free fluid (such as in pipeline, exhaust pipe etc.) or even
It is free air or liquid (such as in open air, water body etc.) projection.Alternatively, can be in 112 (example of sample room
Such as, as shown in Figure 1 one) in analysis sample fluid batch volume 106, using extra conduit or pipeline, valve and/or
Vacuum or pumping arrangement convey the first batch volume 106, and then remove the first batch volume from sample room 112, with standard
The analysis of standby second batch volume.Controller 122 can be incorporated to receive and analyze come self-detector 110 detector data,
Light source 102 is controlled, and alternatively performs what is discussed below in relation to the virtual reconstruction of the align mode of spectroscopic analysis system 100
One or more of operation.
Modulation spectroscopy is also referred to as Harmonic Spectrum, is used for low-down concentration (such as with a few millionths or ten
Hundred million/several scope) sensitively test and analyze the widely used technology of thing.In modulation spectroscopy, the wavelength of light source 102
And/or amplitude is modulated with modulating frequency f.The light launched by lasing light emitter 102 passes through sample gas 106 in path length.When
When light 104 is incided on detector 110, the continuous light beam of light 104 or the intensity of pulse can alternatively change in amplitude.By
The Fourier analysis for the signal that detector 110 produces includes the multiple of the signal component and modulating frequency f at modulating frequency f
The harmonic frequency at (such as 2f, 3f, 4f etc.) place.The demodulation of one of harmonic frequency (such as 2f), which produces, can be used for extremely accurate
Determine the signal of the concentration of one or more analytes in sample fluid 106.By the way that phase-sensitive detection is changed into upper frequency,
Modulation spectroscopy can significantly reduce 1/f noise and realize high sensitivity.Modulation spectroscopy is for detecting and quantifying harmonic analysis thing
Concentration can be extremely sensitive, and can the direct always demodulated signal analyte quantification concentration of self-detector 110.Separately
Outside, the analyte drifted about due to background or instrument can be isolated using lock-in amplifier or other signal filterings or device
In other noises and the absorbance signal that produces.Other spectrographic techniques can include one of these or it is multiple and optional
Other features or process.
Term spectroscopic data refers to quantify in spectroscopic analysis system in response to incident light and sample fluid (such as gas or liquid
Body) interaction of molecules and occur absorbance, reflectivity, fluorescence, scattering or transmitting in one or more data.At this
It is used for the change for the spectroscopic analysis system performance that description may occur due to hardware change over time in open
Term includes frequency registration (FR), it refers to the alignment of the frequency axis (being usually x-axis) of spectroscopic data；Frequency registration bias
(FRD), it typically refers to any change of the frequency axis of the spectroscopic data to being obtained from spectroscopic analysis system or deviation；And frequency
Rate registration index (IFR), it refers to one or more of spectroscopic data spectral signature (for example, peak, paddy, empty crosspoint, flex point
Or another feature point) and/or limit or selected spectral signature between spacing.
Spectroscopic data refers to the one or more spectroscopic data collection collected using spectroscopic analysis system.Live frequency spectrum data is
Refer to using spectrum analysis systematic collection to analyze the spectroscopic data of one or more field samples, and calibration spectrum data refer to
Using spectroscopic analysis system collect with analyze one or more calibration samples spectroscopic data.Field samples are to be used for herein
The term of the fluid (such as gas or liquid) of one or more interested analytes of the finger containing unknown quantity, and calibration sample
It is the sample that one or more analyte concentrations are known or fully characterize.Analyte typically refers to have one or more light
The element or compound of spectrum signature, capture spectroscopic data is configured as its spectroscopic analysis system.Spectral measurement state refers to
The state of the hardware of spectroscopic analysis system when collecting spectroscopic data.
Align mode refers to when spectroscopic analysis system is calibrated, such as when collecting calibration spectrum data, spectrum analysis
The state of the hardware of system.Calibration spectrum data refer to calibrate samples using what spectroscopic analysis system was collected to analyze one or more
This spectroscopic data, the sample have analyte or some other elements or the compound of amount that is known or fully characterizing with
And the optional one or more other known or measurement parameter that fully characterizes is such as such as temperature, pressure, calibration sample
Background composition etc..As it is used herein, function refers to the mathematical operation or mathematical operation for the conversion for causing data set
Set.The example of function is included in the vector or matrix of the value to perform mathematical calculations on spectroscopic data collection.
Regardless of used spectroscopy technology, method consistent with the present invention is usually directed to using one or more schools
The one or more calibrating patterns and/or calibration algorithm that quasi-optical spectrum data set is established in the factory.Such calibration spectrum data
It can be advantageously designed to mathematically represent the concentration model that the field samples analyzed using spectroscopic analysis system are expected to run into
Enclose.Including but not limited to one or more analyte concentration (such as the molal weight of partial pressure, molar fraction, unit volume or rubs
Your number, volume ratio etc.), sample pressure, sample temperature, flow, viscosity etc. the quantitative performances of field samples can be by by one
A or multiple calibrating patterns are calculated or predicted applied to the field samples spectrum of measurement.Occur unless otherwise indicated or with it
Context is inconsistent, and otherwise term " concentration " is generally used for referring to any possible quantitative characteristics listed above.By spectrum analysis
The frequency registration bias for the spectral measurement state that system produces can quantify using similar to method described herein.This amount
The frequency registration bias of change can be used for correcting current spectral measurement state with the original calibrated state of most preferably simulation system,
Concentration can be calculated based on the align mode.
In some favourable realizations of the present invention, it can establish and record for the generally accepted of spectroscopic analysis system
Standard calibration state.For example, the standard calibration state can manufacture the factory of spectroscopic analysis system or assembling place, checkout area
Institute etc. characterization, and can be defined for multiple Individual cells of manufacturer's standard spectroscopic analysis system.With identical correlation
The follow-up measuring state of any spectroscopic analysis system of technical specification can refer to the standard calibration state, so that by similar spectrum
The align mode of analysis system bundles.The single spectroscopic analysis system that the correction of frequency registration bias can operate at the scene
Upper use, to correct its measuring state.Additionally or in the alternative, can in more general level frequency of use registration bias school
Just, the align mode of multiple comparable examples of spectroscopic analysis system is corrected to standard calibration state.
It can include the correction of real-time measuring state with the realization of the present invention come the further advantage realized, it allows
More sane system.The correction of this measuring state can reduce or eliminate degenerate to hardware, drift and/or not reproducible easy
Perception, so as to help to maintain the fidelity of quantitative measurment.The lifetime of system of instrument at the scene can also increase, and reduce visitor
Return goods at family.
It can establish all calibrating patterns as described herein, and can be quantified and school using various Multivariates
Positive frequency registration bias, the multivariable technique include but not limited to classical least square regression (CLS), inverse least square
Return (ILS), principal component analysis (PCA), principal component regression (PCR), Partial Least Squares Regression (PLS), multiple linear regression
(MLR) etc..Quantify can be applied to entirely measurement frequency spectrum or measure one or more parts and sample pressure and the temperature of frequency spectrum
Degrees of data or other relevant measurement data.These multivariate techniques can be drawn by the calculating being embedded in spectroscopic analysis system
Hold up to apply, or applied by the commercially available software of independent in the market, such as held on one or more all-purpose computers
OK.
Correction for the frequency registration bias of spectroscopic analysis system may include one or more spectral shift alignment techniques,
Such as linear deflection, non-linear shift, the stretching for measuring frequency spectrum, compression of measurement frequency spectrum etc..Can be with pure mathematical way
(such as pass through mathematics is performed on the field samples frequency spectrum of collection change), tune via hardware (its can alternatively include but
Be not limited to one or more laser operating temperatures, laser operation electric current (such as nominal current value and/or current slope),
Laser modulation current, demodulation phase, detection phase, modulating frequency, modulating frequency, detection gain etc.), or use Mathematical Correction
Combination with hardware adjustment applies these to correct.Correction can be applied to the whole or single portion of the field samples frequency spectrum of measurement
Point.
In general, realizing according to the present invention, the calculating of analyte concentration can be improved by procedure below：Wherein use
The predetermined calibration model of spectroscopic analysis system carrys out sampling frequency registration bias and correction is applied to live frequency spectrum.As it is following more
It is discussed in detail, calibrating patterns can include calibration algorithm collection, it can be optionally based on what is collected using spectroscopic analysis system
Calibration data set.Alternately, or additionally, calibrating patterns can include being given birth to using empty calibration set as input by computing engines
Into concentration function.Fig. 2 shows the process flow diagram flow chart for the feature for illustrating method consistent with the present invention.It is such at 202
Method includes determining to be applied to the scene obtained using spectroscopic analysis system using calibrating patterns by spectroscopic analysis system
The correction of frequency spectrum.Rectification building-out otherwise corrects the frequency that spectroscopic analysis system occurs relative to previous align mode
Registration bias.Then at 204 the one kind or more with the spectral signature captured in frequency spectrum at the scene is calculated using the correction
The concentration of kind analyte.The description of the realization to the present invention is including more typically one or more of feature is related to these below
Details.
Fig. 3 shows the process flow diagram flow chart of explanation and the feature for realizing consistent method 300 of the present invention.At 302, side
Method 300 includes accessing calibrating patterns, which can include being used for based on the more of calibration spectrum data set in this example
The calibration algorithm collection of the spectroscopic analysis system of variable analysis.One or more calibrating patterns, algorithm, the letter referred in the disclosure
The access of number etc. can usually indicate to prepare other processing that processor or other computer hardwares are discussed to perform, the processing
Device or other computer hardwares can be optionally as a parts for spectroscopic analysis system, or are alternatively configured as and light
One or more remote computing systems of spectrum analysis systems exchange data.In some instances, access can be included from local meter
Calculation machine or machine-readable storage device read one or more calibrating patterns, algorithm, function etc., or can alternatively include logical
Network or other data connections from remote system are crossed to receive this information.It is to be understood that access one or more calibrating dies
Type, algorithm, function etc. are not required because perform it is various calculating and correction processors or other computer hardwares can with or
It is the pre-loaded calibrating patterns, algorithm, the function etc. such as in design time or on startup.
Calibration spectrum data set can be collected to collect the spectrum of various known conditions by using spectroscopic analysis system
Data, in some realizations of the present invention, it, which can be selected from, changes the concentration of one or more analytes, changes pressure or temperature
Degree, the concentration for changing other one or more compounds (in addition to the one or more target analytes), change laser
Operation electric current (for example, nominal current value and/or current slope), change laser operating temperature etc..
Calibration algorithm collection can include one or more models, or can alternatively include together with live spectroscopic data
One or more matrixes (such as vector, vector set etc.), function, the algorithm, statistical tool etc. used, to predict spectrum at the scene
During Data Collection in the frequency registration index and frequency registration bias of spectroscopic analysis system any one or both, and also predict
The concentration for one or more analytes that live frequency spectrum is collected in sample fluid.Calibration algorithm collection be applied at 304 by
Spectroscopic analysis system is the live frequency spectrum that sample fluid is collected, and thus quantifies the frequency registration bias of live frequency spectrum.Can be 306
Place is using the frequency registration bias of quantization to use one or more spectral shift technologies of such as discussed above to come school
Positive scene frequency spectrum.This method further comprises calculating by the concentration of one or more analytes of live frequency spectrum designation at 310.
It is to be understood that the generation of calibration algorithm collection can be " design time from the adjoint description of Fig. 3 and earlier paragraphs
(design time) " processes, such as the process performed in the factory of given spectroscopic analysis system or assembling position.At some
In example, when manufacturing spectroscopic analysis system first and before spectroscopic analysis system comes into operation, calibration can occur and calculate
The generation of method collection.Alternatively or additionally, Mathematical Correction collection can be used as recalibrate or renovate place at, factory,
The part of the recalibration process of the generations such as scene generates.In addition, as described above, calibration algorithm collection can be represented alternatively
The standard calibration state of multiple Physical Examples of the given configuration of spectroscopic analysis system, and can be based on and its used light
Spectrum analysis system different physical spectrum analysis system determines.
The various realizations of the present invention may include to be used to generate Mathematical Correction collection, and pre- for being come using these Mathematical Corrections
Survey the distinct methods of the frequency registration bias for the given live spectroscopic data collection collected by spectroscopic analysis system.Fig. 4, Fig. 6 and Fig. 9
Show process flow diagram flow chart 400,600,900, which illustrate based on the universal method above by reference to Fig. 2 and Fig. 3 explanations and some
The feature of the consistent method of exemplary method.
As shown in the process flow diagram flow chart 400 of Fig. 4, in one approach, it is used to handle at 402 and is given birth to by spectroscopic analysis system
Into the computing device of spectroscopic data can access calibration algorithm collection.As it was previously stated, cause produce calibration algorithm collection process (under
Literary 5 details discussed further of reference chart) it can be performed in design time, it is then loaded into memory or other computer-readable deposits
In reservoir, the memory or computer-readable memory can by spectroscopic analysis system controller 122 or with spectroscopic analysis system phase
Association or other processors access for otherwise receiving the spectroscopic data from spectroscopic analysis system.Such as in Figure 50 0 of Fig. 5
In be further illustrated, calibration algorithm collection 502 in this example be based in design time using computing engines 504 it is unmodified
The input of calibration spectrum data set 506 generate.Unmodified calibration spectrum data set 506 can include by with one
A or multiple variables (such as concentration, pressure, temperature, fluid flow etc.) are analyzed multiple samples on selected change collection and are obtained
Spectroscopic data collection.In the present implementation, it is not necessary to which artificial or mathematics spectral migration is applied to unmodified calibration spectrum data
Collection 506.
Computing engines 504 generate calibration algorithm collection 502, it alternatively includes the index of registering with frequency 508 and concentration 510
Related model or calibration function.Computing engines 504 can be such as using CLS, PCA, PLS, based on unmodified correction
The multi-variables analysis of quasi-optical spectrum data set 506, generation calibration algorithm collection 502.The index model for frequency registration can be used
Carry out the index of pre- measured frequency registration, and can be divided with concentration model to calculate one or more of spectroscopic data at the scene
Analyse the concentration of thing.Alternatively, calibration algorithm can the single model based on spectroscopic analysis system align mode result.In this method
In, it can determine two calibration function (examples for being calculated into the prediction of line frequency registration bias and concentration using calibration algorithm
Such as, calibration vector, calibration matrix etc.), wherein first can be used for the finger that prediction is used for the frequency registration of live spectroscopic data
Mark, and wherein second concentration that can be used for calculating one or more analytes in live spectroscopic data.
See Fig. 4, at 404, the live frequency spectrum data that field samples are collected is calculated as by application calibration algorithm collection 502
Frequency registration characteristic index.For example, index or frequency the registration calibration letter of the frequency registration model discussed in the last period
Several indexs can be applied to live frequency spectrum data.Determined at 406 by the characteristic index of frequency registration and from live frequency spectrum
The index of the measurement of frequency registration is compared, to determine the frequency registration bias of spectroscopic analysis system.The survey of frequency registration
The index of amount can be alternatively the interval between one or more spectral signatures and/or one or more spectral signatures.410
Place, live frequency spectrum is corrected based on frequency registration bias using one or more spectral shift alignment techniques as described above, and
And at 412, concentration model is applied to the live frequency spectrum of correction to calculate the analyte concentration associated with the scene frequency spectrum.
Method such as consistent with Fig. 4, the method shown in the process flow diagram flow chart 600 of Fig. 6 can include being used to locate at 602
Reason accesses the computing device of the spectroscopic data of the spectroscopic analysis system generation of calibration algorithm collection.As it was previously stated, cause to produce school
The process of quasi- set of algorithms 502 can alternatively perform in design time and be then loaded into memory or other computer-readable storages
In device, the memory or other computer-readable memories are can be by spectroscopic analysis system controller 122 or other and spectrum point
Other processors that analysis system is associated or is otherwise received from spectroscopic analysis system spectroscopic data are addressable.Such as exist
It is further illustrated in Figure 70 0 of Fig. 7, the calibration algorithm collection 502 in the example is to be based in design time using computing engines 504
The input generation of calibration spectrum data set 702.However, in this example, calibration spectrum data set 702 includes manually generated
Frequency registration bias spectrum and optionally also unmodified " sky " calibration spectrum data.By being received to using calibration sample
The calibration spectrum applied mathematics of collection is deviated to generate manually generated frequency registration bias spectrum.The output of computing engines 504 is
The model of spectroscopic analysis system align mode, it can be generated calculates letter including frequency registration bias anticipation function 708 and concentration
Both the calibration algorithm collection 502 of number 710.
Referring again to Fig. 6, at 604, frequency registration bias function 708 can be used for quantifying what is collected by spectroscopic analysis system
The measuring state frequency registration bias of live frequency spectrum.Can the measuring state frequency registration bias based on this quantization at 606
The live frequency spectrum of correction, such as use one or more spectral shift alignment techniques as discussed above.At 610, by concentration letter
Number 710 is applied to the live frequency spectrum of correction to calculate the analyte concentration associated with the scene frequency spectrum.
The method consistent with Fig. 6 can also combine the frequency registration bias function 708 generated as shown in Figure 80 0 of Fig. 8
Used with concentration function 710.According to the input of two calibration spectrum data sets 802,804, drawn in design time using calibration
Hold up the calibration algorithm collection 502 in the 504 generations examples.First calibration spectrum data set 802 includes unmodified empty calibration light
Spectrum data set, it does not include manually generated frequency registration bias spectrum.Second calibration spectrum data set 804 includes calibration spectrum
(turn with by one or more of tuning mathematics offset and hardware for example, performing mathematics to the calibration sample frequency spectrum of collection
Change, adjust laser operating temperature, adjustment laser operation electric current, adjustment laser modulation current, adjustment demodulation phase, adjustment
It is any in detection phase, no matter individually or with any combinations) be applied to generate using the calibration spectrum that calibration sample is collected
Manually generated frequency registration bias spectrum.In this illustration, parallel computational model 504A, 504B or alternatively, carry out institute
Single computing engines (not shown in Fig. 8) generation for the serial process that need to be calculated includes frequency registration bias function 708 and (is based on the
The quasi-optical spectrum data set 804 of second revisal) and concentration function 710 (being based on the first calibration spectrum data set 802) calibration algorithm collection 502.
The method shown in the process flow diagram flow chart 900 of Fig. 9 is directed to use with one or more confidence indexs.Confidence index is
The statistical tool of one or more in-site measurement samples can how well be covered for describing calibrating patterns.In the reality of the present invention
In existing, it can determine most preferably to match measuring state needed for the storage expression of actual alignment state using confidence index
Necessary measuring state changes.The example for the confidence target function that can be used by this way include but not limited to compose residual error,
Mahalanobis distance, variance index (such as mean square error, root-mean-square error, R squares etc.), etc..In design time, by computing engines
504 use the empty calibration set 1002 as shown in Figure 100 0 of Figure 10 to generate concentration function (or concentration model) 710 as input.
Calibration function 710 can be loaded into memory or by spectroscopic analysis system controller 122 or associated with spectroscopic analysis system
Other processors may have access to or otherwise from spectroscopic analysis system receive spectroscopic data memory or other calculating
In machine readable memory.
As shown in figure 9, at 902, this method can include being used to handle the spectroscopic data generated by spectroscopic analysis system
Computing device, the system access include one or more calibration functions 710 concentration model.At 904, mathematically change existing
The frequency registration bias of sample spectra are to produce the change of the predetermined number as shown in the chart 1100 of Figure 11.These mathematics
Change the linearly or nonlinearly spectral shift that can include live frequency spectrum, stretching, compression etc..At 906, for live frequency spectrum
Before each change calculates one or more confidence indexs, concentration model 710 is applied to all predetermined quantities of live frequency spectrum
Change.It is the monotropic of frequency registration bias by the compositional modeling of each confidence index or more than one confidence index at 910
Flow function so that mathematically determine to minimize or the optimum frequency of the combination of maximization confidence index or confidence index registration is inclined
Difference, as shown in the chart 1200 of Figure 12.At 912, concentration function 710 is applied to the spy corresponding to optimum frequency registration bias
Fixed scene spectral change, to calculate the analyte concentration associated with the scene frequency spectrum, because corresponding to optimum frequency registration partially
Difference specific change be and the most matched change of the original calibrated state of spectroscopic analysis system.
Fundamental Digital Circuit, integrated circuit, application-specific integrated circuit (ASIC), the field programmable gate specially designed can be used
Array (FPGA) computer hardware, firmware, software and/or its combination come realize the present invention one or more aspects or feature.
These different aspects or feature can include can perform on programmable systems and/or interpretable one or more computers
Realization in program, the programmable system include at least one programmable processor, it can be special or general, coupling
Close to receive from storage system, the data of at least one input unit and at least one output device and instruction and by data
Storage system, at least one input unit and at least one output device are transferred to instruction.
These can also be referred to as the computer journey of program, software, software application, application program, component or code
Sequence includes machine instructions for programmable processors, and can be with high level procedural, the programming language of object-oriented, work(
Can property programming language, logic programming language and/or compilation/machine language realization.As it is used herein, term is " machine readable
Medium " refers to be used to machine instruction and/or data being supplied to programmable processor, including receives as machine-readable signal
Any computer program product, equipment and/or the device of the machine readable media of machine instruction, such as disk, CD, deposit
Reservoir and programmable logic device (PLD).Term " machine-readable signal " refers to be used to refer to programmable processor offer machine
Order and/or any signal of data.Machine readable media can with nonvolatile store such machine instruction, such as non-
Transient state solid-state memory or magnetic hard drive or any equivalent storage medium are such.Machine readable media can be alternatively
Or additionally with transient fashion store as machine instruction, such as processor cache or with one or more physics
Other random access memory that processor core is associated.
Interacted to provide with user, one or more aspects of the invention or feature can be with display device
Realized on computer, be such as used for the cathode-ray tube (CRT) or liquid crystal display (LCD) or hair that information is shown to user
Optical diode (LED) monitor and user can provide the keyboard and pointing device (such as mouse of input by it to computer
Or trace ball).Other kinds of device may also be used for providing and be interacted with user.For example, it is supplied to the feedback of user can be with
It is any type of sensory feedback, such as visual feedback, audio feedback or touch feedback；And it can in any form receive and
From the input of user, include but not limited to acoustics, voice or sense of touch.Other possible input units include but not limited to touch
Screen or other touch sensitive devices are touched, such as single-point or multi-point electric resistance or capacitive touch control plate, speech recognition hardware and software, optics are swept
Retouch instrument, optical pointer, digital image capture device and associated translation software etc..Computer away from analyzer can pass through
Wired or wireless network is connected to analyzer, to realize the data exchange between analyzer and remote computer (for example, from analysis
Instrument receives the data of remote computer and transmits the information such as calibration data, operating parameter, software upgrading or renewal) and point
The remote control of analyzer, diagnosis etc..
In described above and claim, such as the phrase of " at least one " or " one or more " can be adjoint later
The connection list of element or feature and occur.Term "and/or" can also appear in two or more elements or the row of feature
In table.Unless the other contradicted by context that impliedly or is clearly used with it, otherwise such phrase is intended to indicate that independent row
Any one in the element or feature that go out or any element enumerated or feature and any other element enumerated or feature
Combination.For example, phrase " at least one in A and B ", " one or more of A and B " and " A and/or B " are each intended to
Represent " A is independent, B is independent or A and B together ".Similar explanation is also applied for the list for including three or more projects.For example,
Phrase " at least one in A, B and C ", " one or more of A, B and C " and " A, B and/or C " are each intended to indicate that " A
Individually, B is independent, C is independent, A and B together, A and C together, B and C together or A and B and C together ".Wanted above and in right
The use of middle term "based" is asked to be intended to indicate that " being based at least partially on " so that unrequited feature or element is also permissible
's.
The present invention can depend on desired configuration and be lost in system, equipment, method and/or article.Preceding
The realization illustrated in the description in face does not represent all realizations consistent with the present invention.On the contrary, they be only with it is described
Some consistent examples of invention related aspect.Although some modifications are described in detail above, other are changed or add
It is also possible to add.Specifically, in addition to those, other feature and/or modification can also be provided except set forth herein.Example
Such as, implementations described above can be directed to disclosed feature various combinations and sub-portfolio and/or it is disclosed above it is some its
The combination of his feature and sub-portfolio.In addition, shown in logic flow describing in the accompanying drawings and/or described herein is not necessarily required to
Particular order or even the order of sequence realizes desired result.Other realizations can be within the scope of the appended claims.
Claims (37)
1. a method of computer implementation, including：
When the spectroscopic analysis system of sample fluid deviates standard calibration state, quantify the spectroscopic analysis system during analysis
The frequency registration bias of the live frequency spectrum of collection；
The frequency registration bias correction live frequency spectrum is based on using at least one spectral shift technology；And
The concentration of the analyte by the live frequency spectrum designation is calculated using calibrated live frequency spectrum.
2. computer implemented method as claimed in claim 1, wherein the amount of the frequency registration bias to the live frequency spectrum
Changing includes calibration algorithm collection to be applied to the live frequency spectrum.
3. computer implemented method as claimed in claim 1, wherein the amount of the frequency registration bias to the live frequency spectrum
Change and include the use of at least one frequency registration bias function that calibration algorithm concentration includes.
4. the computer implemented method as any one of claim 2 to 3, wherein the calibration algorithm collection includes being used for
The concentration function of the spectroscopic analysis system；And wherein described quantization includes：
Mathematically change the frequency registration bias of the live frequency spectrum to produce the change of predetermined quantity；
After the concentration function being applied to all changes of the live frequency spectrum, each change to the live frequency spectrum
Calculate one or more confidence indexs；And
The one-variable function that the compositional modeling of each confidence index or more than one confidence index is frequency registration bias so that
Mathematically determine to minimize the combination of the confidence index or more than one confidence index or maximumlly optimum frequency is registering
Deviation.
5. computer implemented method as claimed in claim 4, wherein the concentration function is manually generated based on not including
Frequency registration bias spectrum unmodified calibration spectrum data set.
6. the computer implemented method as any one of claim 4 to 5, wherein the calculating of the concentration of the analyte
Including the concentration function being applied to the live spectral change corresponding to the optimum frequency registration bias.
7. the computer implemented method as any one of claim 2 to 6, wherein the calibration algorithm collection includes being based on
Represent the output of the computing engines of the multi-variables analysis of the calibration data set of the standard calibration state of the spectroscopic analysis system.
8. computer implemented method as claimed in claim 7, wherein the calibration data set includes manually generated frequency
Registration bias spectrum, the frequency registration bias spectrum are the calibration light by the way that mathematics offset applications are collected in use calibration sample
Compose and generated in design time.
9. the computer implemented method as any one of claim 2 to 8, wherein matching somebody with somebody to the frequency of the live frequency spectrum
The quantization of quasi- deviation includes：
The characteristic index of the frequency registration of the live frequency spectrum is calculated using the calibration algorithm collection；And
By the way that the characteristic index measurement index registering with the frequency determined from the live frequency spectrum is compared to quantify
The frequency registration bias of the scene frequency spectrum.
10. computer implemented method as claimed in claim 9, wherein the measurement index of frequency registration including one or
Interval between multiple spectral signatures and/or one or more of spectral signatures.
11. the computer implemented method as any one of claims 1 to 10, wherein the correction includes：
The live frequency spectrum is corrected using measuring state frequency registration bias of at least one spectral shift technology based on quantization.
12. computer implemented method as claimed in claim 11, wherein at least one spectral shift technology includes line
Property offset, non-linear shift, the stretching for measuring frequency spectrum and at least one of the compression for measuring frequency spectrum.
13. the computer implemented method as any one of claim 11 to 12, further includes with following one kind or more
Plant to apply at least one spectral shift technology：Pure mathematics mode, tunes via hardware, and by using Mathematical Correction
With the combination of hardware tuning.
14. the computer implemented method as any one of claim 1 to 13, wherein at least one spectral shift skill
Art is applied to one or more particulars of whole scene frequency spectrum or the live frequency spectrum.
15. the computer implemented method as any one of claim 1 to 14, wherein the spectroscopic analysis system includes
Following at least one：Absorption spectroanalysis system, emission spectrographic analysis system, spectrofluorimetry system, Fourier transformation
Infrared spectrum analysis system, non-dispersive infrared (NDIR) spectroscopic analysis system, chamber enhanced spectrum analysis system, cavity ring-down spectroscopy point
Analysis system, collection coelosis output spectrum analysis system, photoacoustic spectroscopy system and Raman spectrum analysis system.
16. the computer implemented method as any one of claim 1 to 15, wherein the spectroscopic analysis system includes
Sample room, for accommodating the sample fluid while light beam passes through the sample fluid at least once.
17. the computer implemented method as any one of claim 1 to 15, wherein the spectroscopic analysis system includes
Free space volume, while light beam passes through the sample fluid at least once, the sample fluid is positioned at described freely empty
Between in volume.
18. a kind of system, including：
It is configured as performing the computer hardware of operation, including：
When the spectroscopic analysis system of sample fluid deviates standard calibration state, quantify the spectroscopic analysis system during analysis
The frequency registration bias of the live frequency spectrum of collection；
The frequency registration bias correction live frequency spectrum is based on using at least one spectral shift technology；And
The concentration of at least one analyte by the live frequency spectrum designation is calculated using calibrated live frequency spectrum.
19. system as claimed in claim 18, further includes the spectroscopic analysis system, the spectroscopic analysis system includes laser
At least one of light source and non-laser light source and the detector for quantifying the live frequency spectrum, the laser light source and described non-
Laser light source is arranged to pass the beam through the sample fluid at least once.
20. system as claimed in claim 19, wherein the spectroscopic analysis system includes lasing light emitter, under the lasing light emitter includes
The one or more stated：Semiconductor laser, tunable diode laser, quantum cascade laser, with interior cascaded laser,
Horizontal cavity emitting laser, vertical-cavity-face emitting semiconductor laser, distributed feedback laser, distribution Bragg reflection device laser
Device, external-cavity diode laser, gas discharge laser, liquid laser and solid state laser.
21. system as claimed in claim 19, wherein the spectroscopic analysis system includes the non-laser light source, it is described non-sharp
Radiant includes following one or more：Light emitting diode, incandescent source, heat source, discharge source, laser assisted light source, laser
The plasma source of driving, fluorescence source, super generating light source, spontaneous emission (ASE) source of amplification, super continuous source, wide spectral sources and
Wide tunable QCL sources with adjustable grid type waveguide filter.
22. the system as any one of claim 18 to 21, wherein the spectroscopic analysis system further includes sample room, is used
In light beam through the sample fluid at least once while accommodate the sample fluid.
23. the system as any one of claim 18 to 21, wherein the spectroscopic analysis system further includes free space
Volume, while light beam passes through the sample fluid at least once, the sample fluid is located in the free space volume.
24. the system as any one of claim 18 to 23, wherein to the frequency registration bias of the live frequency spectrum
Quantify to include calibration algorithm collection to be applied to the live frequency spectrum.
25. the system as any one of claim 18 to 23, wherein to the frequency registration bias of the live frequency spectrum
Quantify to include the use of at least one frequency registration bias function that calibration algorithm concentration includes.
26. the system as any one of claim 24 to 25, wherein the calibration algorithm collection includes being used for the spectrum
The concentration function of analysis system；And wherein described quantization includes：
Mathematically change the frequency registration bias of the live frequency spectrum to produce the change of predetermined quantity；
After the concentration function being applied to all changes of the live frequency spectrum, become for each of live frequency spectrum
Change and calculate one or more confidence indexs；And
The one-variable function that the compositional modeling of each confidence index or more than one confidence index is frequency registration bias with number
Determine with learning to minimize the combination of the confidence index or more than one confidence index or maximumlly optimum frequency registration is inclined
Difference.
27. system as claimed in claim 26, wherein the concentration function is registering based on manually generated frequency is not included
The unmodified calibration spectrum data set of deviation spectrum.
28. the system as any one of claim 26 to 27, wherein the calculating of the concentration of the analyte is included institute
State the live spectral change that concentration function is applied to correspond to the optimum frequency registration bias.
29. the system as any one of claim 22 to 28, wherein the calibration algorithm collection is included based on described in representative
The output of the computing engines of the multi-variables analysis of the calibration data set of the standard calibration state of spectroscopic analysis system.
30. system as claimed in claim 29, wherein the calibration data set includes manually generated frequency registration bias light
Spectrum, which is by the way that mathematics offset applications are being designed in the calibration spectrum collected using calibration sample
What the time produced.
31. the system as any one of claim 22 to 30, wherein to the frequency registration bias of the live frequency spectrum
Quantization includes：
The characteristic index of the frequency registration of the live frequency spectrum is calculated using the calibration algorithm collection；And
By the way that the characteristic index measurement index registering with the frequency determined from the live frequency spectrum is compared to quantify
The frequency registration bias of the scene frequency spectrum.
32. system as claimed in claim 31, wherein the measurement index of frequency registration includes one or more Spectral Properties
Interval between sign and/or one or more of spectral signatures.
33. the system as any one of claim 18 to 32, wherein the correction includes：
Use measuring state frequency registration bias correction of at least one spectral shift technology based on the quantization scene frequency
Spectrum.
34. system as claimed in claim 33, wherein at least one spectral shift technology includes linear deflection, non-linear
At least one of offset, the stretching of the measurement frequency spectrum and compression of the measurement frequency spectrum.
35. the system as any one of claim 33 to 34, further include by it is following it is one or more in a manner of be applied to
A kind of few spectral shift technology：Pure mathematics mode, tunes via hardware, and the group tuned by using Mathematical Correction and hardware
Close.
36. the system as any one of claim 18 to 35, wherein at least one spectral shift technology is employed
In whole scene frequency spectrum or one or more particulars of the live frequency spectrum.
37. a kind of computer program product of the machinable medium including coded command, described instruction by one or
Multiple programmable processors make one or more of programmable processors perform operation when performing, and the operation includes：
When the spectroscopic analysis system of sample fluid deviates standard calibration state, quantify the spectroscopic analysis system during analysis
The frequency registration bias of the live frequency spectrum of collection；
The frequency registration bias correction live frequency spectrum is based on using at least one spectral shift technology；And
The concentration of at least one analyte by the live frequency spectrum designation is calculated using calibrated live frequency spectrum.
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| PCT/US2016/045259 WO2017023978A1 (en) | 2015-08-03 | 2016-08-03 | Determination and correction of frequency registration deviations for quantitative spectroscopy |
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| US9696204B2 (en) * | 2015-08-03 | 2017-07-04 | Spectrasensors, Inc. | Determination and correction of frequency registration deviations for quantitative spectroscopy |
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| EP3488204A4 (en) | 2016-07-20 | 2020-07-22 | Verifood Ltd. | Accessories for handheld spectrometer |
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| CN107949775B (en) | 2021-04-06 |
| US9696204B2 (en) | 2017-07-04 |
| US20170038257A1 (en) | 2017-02-09 |
| WO2017023978A1 (en) | 2017-02-09 |
| US10180353B2 (en) | 2019-01-15 |
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| EP3332231B1 (en) | 2023-03-08 |
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